Naphthofuranedione vat dyestuffs



MAM;

United States Patent() 2,976,287 7 NAPHTHOFURANEDIONE VAT ,DYESTUFFS "David I. Randall, New 'Vernon, and Wilhelm Schmidt- Nickels, Little York, N.J., assignors to General Aniline & Film Corporation, New York, N.'Y., a corporation 7 of Delaware No Drawing. Filed Dec. 3, 19ss,.ser. No.,777,s2"1

8 Claims. (Cl. 260249.6)

This invention relates to novel heterocyclic vat .dyestuffs having the formula p in which one adjacent pair of valencesarebondefl to hydrogen atoms, the other adjacent pair 'of Y valences are bonded to a radical of the formula fi on and the -NH- group is bonded in one of the a posier phenol, naphthol :or 'a lower alkyl or alkoxy substituted derivative thereof, n being an integer of 1 to 3.

The above dyestufr' intermediates having the formula and methods for their manufacture zareidisclosedlin our copending application Serial No. 774,169, zfiled $11 .No-

'ivember 17, 1958. These dyestu'tf intermediates,dis- 70 :closed :in said application, are prepared :by reacting 1 uncle of '8-nitro-2,3-dichloro- 1-4-naphthoquinone with 1;

2,976,287: Patented Mar. 21, 1961 mole of l-naphthol or Z-naphthol in the presence of an alkaline acid binding agent, followed by the step of'reducing the nitro groups in the resulting product to amino groups, as by treatment with sodium hydrosulfite. The initial reaction always produces a dual component mixture of isomers in one of which the nitro group is bonded in one or position and in the other of which the nitro group is bonded in the other a position. This isomeric mixture may be subjected to reduction to produce a mixture of the corresponding amino-substituted isomers, or the isomers in said isomeric mixture may first be soparated from each other in known manner, as 'byifractional precipitation, fractional crystallization, vacuum sublimation or chromatographic adsorption, as disclosed in said application after which each of the separated isomers may be reduced to the corresponding amino-substituted intermediate. It will be understood that the dyestuff intermediate employed in the process of thepresent invention may be a single isomer in which the amino group is bonded in either of the at positions shown, or preferably, a mixture of such isomers.

Where only one or two moles of said dyestuif intermediate (n is one or two) are reacted with '1 mole of the cyanuric chloride in accordance with the present "invention, the remaining reactive chlorine atoms in the cyanuric chloride are reacted with, respectively, 2 or 1 mole of phenol, naphthol, or a lower alkyl or lower alkoxy substituted derivative thereof. Such derivatives may contain from 1 to 3 nuclearly substituted lower alkyl groups such as methyl or ethyl or lower alkoxy groups such as methoxy or ethoxy. Either l-naphthol or 2-naphthol may be employed as the naphthol reactant in .the present process. Examples of such substituted reactant include 1-methyl-2-naphthol, Z-methyl-I-naphthol, 2,3-, 6-, and 3,5-dimethoxy phenols, xylenol, 0-, m-, and pmethyl, methoxy, ethyl and ethoxy phenols, Z-methoxy- 4-methyl phenol and 2,4,5- and 2,4,6-trimethyl phenols.

When three moles of said dyestufi intermediate (single isomer or mixture of isomers) are reacted with one mole of cyanuric chloride the reaction is preferably carried :out in the presence of an inert organic diluent such as aromatic hydrocarbon or halogenated.hydrocarbonor-ga phenol or naphthol. As representative of such diluents,

there may be mentioned nitrobenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, naphthalene, meta or para cresol, phenol, 1- or 2-naphthol or the like. The phenols and naphthols are in this instance inert to the reaction which is preferential betweenthe cyanuric chloride and the said dyestufi intermediate.

When only one or two moles of the said dyestuif intermediate are reacted with each mole or cyanuric chloride,

the remaining reactive chlorine atoms in the cyanuric chloride molecule are reacted with, respectively, ,2, or. ,1

mole of the said phenol or naphthol reactant. 'Inthis simultaneously as the sole diluent.

The reaction is preferably carried out in a non-aqueoiis .medium and, if desired, in the presence of an alkaline acid binding agent such as sodium carbonate, potassium ,carbonate or the like. Elevated reaction tempera'tures are employed, generally ranging from about lDO'LICr p to the boiling point of'the reaction medium. The optimum temperature in any particular instance will be readily ascertainable by the worker skilled in the .art.

The novel vat dyestuffs of this invention generally yield red to orange shades on cotton and other fibers having good to'excellent fastness propertiesto washing,

chlorine and/or light.

The following examples, in which parts :areby weight, t I unless otherwise indicated, are illustrative of the instant 1;; a

invention and are not to be regarded as lirnitativer,

3 Example 1 A charge of 350 cc. of a mixture of mand p-cresols, 5.10 g. of the binary mixture of isomeric compounds of the structure:

in one of which the H N-group is bonded in one a position and in the other of which the H N-group is bonded in the other a position (prepared as described in Example 2 of said copending application by reaction of 1 mole of 8-nitro-2,3-dichloronaphthoquinone with 1 mole of 2- .naphthol followed by reduction of the nitro groups in the resulting binary isomeric mixture) and 0.80 g. of cyanuric chloride is heated to 118 C. over 5 /2 hours, held at about this temperature for 1% hours and then refluxed for 2 hours. The reaction product is filtered oil at room temperature, washed with acetone and dried.

The product is obtained in the form of hard dark lumps. It vats readily to a brilliant orange vat, dyeing cotton in a strong, fairly bright scarlet shade. It is a mixture of the four possible isomeric compounds of the formula:

#N a ll Exam le 2 The process of Example 1 is repeated except that the compounds in the binary mixture of isomers employed therein have the structure HaN in one of which the H N-group is bonded in one on position, and in the other of which the H N-group is bonded in the other a position (prepared as decribed in Example 1 of said copending application, by reaction of 1 mole of 8-nitro-2,3-dichloronaphthoquinone with 1 mole of 1- naphthol followed by reduction of the nitro groups in the resulting binary isomeric mixture). 7

Similar results are obtained, the compounds in the resulting mixture having the formula 4 Example 3 A charge of 200 g. of phenol and 5.0 g. of the binary mixture of isomeric compounds employed in Example 1 is heated to about 110 C. after which 1.8 g. of cyanuric chloride is added. The mixture is maintained at 105 to 110 C. for about 2 hours and then refluxed for about 3 hours. The resulting mixture is diluted with acetone at 120 C. to precipitate the dyestufi product which is then filtered oif at room temperature, washed with acetone to a colorless wash, and dried.

The product vats readily, dyeing cotton in a strong, bright, reddish orange shade of good light fastness and chlorine fastness. It is a mixture of the three possible isomeric compounds of the formula This invention has been disclosed with respect to cer tain preferred embodiments, and various modifications and variations thereof will become obvious to the per- 30 son skilled in the art. It is to be understood that such modifications and variations are to be included within the spirit and purview of this application and the scope of the appended claims.

This application is a continuation-in-part of our copending application Serial No. 556,414, filed on December 30, 1955, now US. Patent 2,870,168.

We claim:

1.'A process comprising reacting by heating at a temperature ranging from about 100 C. up to the boiling 40 point of the reaction medium 1 mole of cyanuric chloride with 3 moles of a dyestufi intermediate of the formula in which the l-l N-group is bonded in one of the a positions shown.

2. A process comprising reacting by heating at a temparature ranging from about 100 C. up to the boiling point of the reaction medium 1 mole of cyanuric chloride with 3 moles of a dyestuff intermediate of the formula MA ..i

5 v v6 ride with 2 moles of a dyestufi intermediate of the forand mula o 0 HaN V and the group is bonded in one of the oc positions shown, and R and R are selected from thegroup con sisting of R phenoxy and naphthoxy.

5. Compounds of the formula in which the H N-group is bonded in one of the a positions shown, and 1 mole of phenol. 5

4. Compounds of the formula -40 I wherein each :group is bonded in one of the a t positions .shown.

6. Compounds of the formula wherein R is selected from the group consisting of u 7 1 0 t 1,; NH wherein each -NH- group is bonded bone of the u I positions shown. s e/ I p 0 7. Compounds of the formula and HrN

wherein the ---NH;, group is bonded in one of the at positions shown, and 3-11 moles of a member selected from the group consisting of phenol, naphthol and lower alkyl and lower alkoxy substituted derivatives thereof, n being an integer of from 1 to 3.

References Cited in the file of this patent UNITED STATES PATENTS Schmidt-Nickels et a1. Dec. 2, 1958 Schmidt-Nickels Dec. 2, 1958 Randall et al. Jan. 20, 1959 

4. COMPOUNDS OF THE FORMULA
 5. COMPOUNDS OF THE FORMULA 